EP1123270B1 - Preparation d'amines - Google Patents

Preparation d'amines Download PDF

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Publication number
EP1123270B1
EP1123270B1 EP99958664A EP99958664A EP1123270B1 EP 1123270 B1 EP1123270 B1 EP 1123270B1 EP 99958664 A EP99958664 A EP 99958664A EP 99958664 A EP99958664 A EP 99958664A EP 1123270 B1 EP1123270 B1 EP 1123270B1
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EP
European Patent Office
Prior art keywords
water
catalyst
fthf
ammonia
aldehyde
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP99958664A
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German (de)
English (en)
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EP1123270A1 (fr
Inventor
Clyde Neal Clubb
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Eastman Chemical Co
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Eastman Chemical Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/12—Radicals substituted by oxygen atoms

Definitions

  • This invention pertains to a novel process for the preparation of amines by contacting a water-soluble aldehyde with ammonia and hydrogen in the presence of a catalyst. More specifically, this invention pertains to the synthesis of amines by contacting an aqueous solution of a water-soluble aldehyde with ammonia and hydrogen at elevated temperature and pressure in the presence of certain ruthenium catalysts.
  • U.S. Patents 4,963,672 and 5,068,398 describe the reductive amination of 5-formylvalerates in liquid ammonia using a supported ruthenium catalyst. These patents teach that the disclosed processes are carried out at relatively high total pressures of 40 to 100 bar (580 to 1450 pounds per square inch - psi; or 4,000 to 10,000 kPa). The examples contained in the patents employed total pressures of 98 to 99 bar (9,800 to 9,900 kPa).
  • U.S. Patent 5,068,398 discloses a comparative example that demonstrates leaching of nickel from a supported nickel catalyst.
  • Patent 5,166,443 describes a two-step process wherein certain 2,2-disubstituted-4-cyanobutanal compounds are converted to their corresponding diamines.
  • the first step involves treating the cyanobutanal with ammonia in the presence of an acidic heterogeneous catalyst.
  • the resulting material then is fed to a hydrogenation zone which preferably uses a ruthenium catalyst.
  • the pressures are relatively high at 50 to 500 bar (725-7250 psi; or 5,000 to 50,000 kPa), preferably 100 to 350 bar (10,000 to 35,000 kPa) and most preferably from 150 to 300 bar (15,000 to 30,000 kPa).
  • the hydrogenation zone is operated at a pressure of 200 or 250 bar (20,000 to 25,000 kPa).
  • the FTHF from which AMTHF may be prepared preferably is used in the form of an aqueous solution.
  • FTHF may be prepared by hydroformylation of 2,5-dihydrofuran in the presence of a rhodium-phosphine catalyst and an organic, water-immiscible, hydroformylation solvent. Recovery of FTHF by distillation in the presence of the hydroformylation solvent results in the formation of hemiacetal oligomers and an overall significant yield loss.
  • the FTHF product preferably is recovered by first extracting the hydroformylation product solution with water to produce an aqueous solution of FTHF.
  • This aqueous solution of FTHF in chemical processes wherein the FTHF is converted to other compounds such as AMTHF is a particularly efficient means for producing such other compounds.
  • European Patent EP 0 663 389 A1 describes a process for the preparation of aminoalcohols. The process uses a ruthenium catalyst to accomplish the reductive amination of hydroxycarbonyl compounds.
  • AMTHF can be produced in good yields and conversions from FTHF and ammonia in the presence of water using a catalyst comprising ruthenium on a catalyst support material and relatively mild conditions of pressure and temperature.
  • a supported ruthenium catalyst has been found to avoid the problem presented by the presence of catalyst particulate matter during product isolation and purification. It is believed that this discovery has a more general application to the conversion of water-soluble aldehydes to amines by reductive amination in the presence of water.
  • this discovery can be applied to aqueous aldehyde solutions where aqueous extraction is used to isolate the aldehyde from a hydroformylation product solution comprising a water-soluble aldehyde, catalyst components and a hydroformylation solvent.
  • Typical catalyst systems are those employed in hydroformylation and may be applied to the preparation of multifunctional amines such as 4-amino-1-butanol and neopentanolamine from water- soluble aldehydes such as 4-hydroxybutanal and hydroxypivaldehyde, respectively.
  • the present invention therefore provides an improved process for the preparation of an amine from a water-soluble aldehyde which comprises contacting in a reaction zone a water-soluble aldehyde, water, ammonia and hydrogen in the presence of a supported ruthenium catalyst.
  • the supported ruthenium catalyst has been found to exhibit activity and selectivity comparable to the nickel catalysts but without leaching or dissolution into the reaction medium.
  • the ruthenium catalyst permits the use of aqueous solutions of the water-soluble aldehyde and/or aqueous ammonia (ammonium hydroxide) to make an amine under mild reductive amination conditions with easy isolation of the amine by simple distillation. Additionally, the relatively mild operating conditions useful in the present process provide obvious economic and safety advantages over a higher pressure system.
  • AMTHF is a valuable and useful intermediate in the synthesis of pesticides. See, for example, Japanese Patent Publications 10-045739 A2, 09-110848 A2, 09-012565 A2, 08-311063 A2, 08-291170 A2, 08-269053 A2, 08-295684 A2, 08-269035 A2, 08-269034 A2, 08-259553 A2, 08-269052 A2, 08-259554 A2, 08-259563 A2, 08-176132 A2 and 07-173157 A2 and European Patent Application EP 649845 A1.
  • the FTHF used in the present process may be obtained by hydroformylating 2,5-dihydrofuran (2,5-DHF) using a conventional rhodium-phosphine catalyst.
  • 2,5-DHF may be obtained from 1,3-butadiene by the steps of (1) partially oxidizing butadiene to 3,4-epoxy-1-butene and (2) isomerizing the 3,4-epoxy-1-butene to 2,5-DHF.
  • the selective oxidation of butadiene to 3,4-epoxy-1-butene may be accomplished by the processes described in U.S. Patents 5,117,012, 5,312,931 and 5,362,890.
  • the isomerization of 3,4-epoxy-1-butene to 2,5-DHF may be carried out according to the processes disclosed in U.S. Patents 5,082,956 and 5,315,019.
  • the process for producing amines in accordance with the present invention is carried out by contacting in a reaction zone a water-soluble aldehyde, water, ammonia and hydrogen in the presence of a supported ruthenium catalyst.
  • the amount of water present typically will give a water:aldehyde weight ratio of 0.1:1 to 10:1, preferably 0.2:1 to 2:1.
  • the amount of ammonia present in the reaction zone can vary substantially and normally will be an amount which gives an ammonia:aldehyde mole ratio of at least 1:1, preferably 2:1 to 20:1, and most preferably 5:1 to 10:1.
  • the process may be carried out at a temperature of at least 40°C, preferably 60 to 150°C and most preferably 70 to 120°C.
  • the total reaction pressure is at least 7 bar absolute (bara)(700 kPa), preferably in the range of about 7 to 50 bara and most preferably in the range of 10 to 30 bara (1,000 to 3,000 kPa).
  • a catalyst comprising ruthenium deposited on a catalyst support material.
  • suitable support materials include carbon, aluminum oxide, silica gel, titanium dioxide, zirconium dioxide, magnesium aluminates and magnesium silicates. Carbon is the preferred support.
  • the amount of ruthenium on the supported catalysts may be in the range of 0.1 to 10 weight percent, preferably 5 to 9 weight percent, based on the total weight of the supported catalyst.
  • the catalysts used in the process preferably contain only ruthenium as the catalytically active metal, i.e., the catalysts consist essentially of ruthenium deposited on a catalyst support material.
  • the water-soluble aldehydes which may be used in the process of the present invention may contain up to 10 carbon atoms and may be acyclic or cyclic, carbocylic or heterocyclic, provided that they are water-soluble, i.e., have a water solubility of at least 2 g per liter water, preferably at least 20 g per liter water.
  • the water-soluble aldehydes may exist in aqueous solution in the form of hydrates of the aldehyde.
  • aldehydes it may be advantageous to employ a water-miscible co-solvent such as an alkanol, e.g., methanol, ethanol and 2-propanol, to facilitate or increase the solubility of an aldehyde reactant in water.
  • aldehydes which may be used in the process include 3- and 2-formyltetrahydrofuran, 3-hydroxy-2,2-dimethylpropanal, 3-hydroxy-2-methylpropanal, 4-hydroxybutanal, 3-hydroxybutanal, 3-hydroxypropanal, n-butyraldehyde, isobutyraldehyde, propanal, and acetaldehyde.
  • the process is particularly useful for the preparation of AMTHF from FTHF.
  • the process may be carried out in a batch, semi-continuous or continuation mode of operation using procedures and techniques well-known in the industry.
  • ammonia and hydrogen may be fed to a pressure vessel containing an aqueous solution of a water-soluble aldehyde and the supported ruthenium catalyst either as a slurry or contained in a wire mesh basket.
  • the catalyst typically is used in such batch operation in an amount which gives a catalyst:aldehyde weight ratio of at least 0.01:1, typically in the range of 0.05:1 to 0.5:1 and preferably in the range of 0.1:1 to 0.2:1.
  • the catalyst may be used in the form of a powder or as pellets or extrudates.
  • ammonia, hydrogen and an aqueous solution of a water-soluble aldehyde may be fed to a pressure vessel, or to a series of pressure vessels, containing one or more fixed beds of a supported catalyst, e.g., a ruthenium-on-carbon catalyst.
  • the reactant solution flows over and through the supported catalyst in the presence of ammonia and hydrogen at elevated pressure and temperature to convert the aldehyde to an amine. While not being bound to any particular theory, it is thought that the conversion of the aldehyde to the amine proceeds via an imine intermediate produced by the reaction of the aldehyde and ammonia. It is important that the imine is hydrogenated quickly to the desired amine product before other reactions occur.
  • Anhydrous FTHF (23.4 g, 0.23 mol), ammonium hydroxide (135g, 29.3% NH 3 , 2.3 mol), and molybdenum-promoted Raney-type nickel powder (5.0g wet) were heated to 60°C and 21 bara (300 psi; or 2,100 kPa) hydrogen for 2 hours.
  • the resulting solution was filtered to remove the catalyst. Removal of most of the water and ammonia by distillation of an aliquot left an oil with a suspended solid. Filtration gave a green powder.
  • Anhydrous FTHF (25.8 g, 0.26 mol) and ammonium hydroxide (135 g, 29.3% NH 3 , 2.3 mol) were heated to 100°C and 21 bara (300 psi; or 2,100 kPa) hydrogen pressure for 5.5 hours in the presence of a 7% ruthenium on carbon catalyst (5.0 g) suspended in a basket.
  • Analysis of the resulting solution by gas chromatography showed 90% AMTHF, 4.7% 3-hydroxymethyltetrahydrofuran (HMTHF) and 1.0% di-(tetrahydro-3-furanmethyl)-amine (DTFMA).
  • the following examples demonstrate continuous operation of the process wherein an aqueous solution of FTHF (55-59 weight percent concentration), anhydrous ammonia, and hydrogen were fed to a 21 element in-line mixer at the base of a tube-in-shell reactor loaded with catalyst and inerts.
  • the reactor comprised stainless steel tubing having an interior diameter of 21.2 mm (0.834 inch) positioned within a pipe having an interior diameter of 38 mm (1.5 inch) and equipped with inlet and outlet ports for a heating liquid.
  • the catalyst and inerts were placed in the reactor tube between two screens 53.3 cm (21 inches) apart. Thermocouples in a thermowell in the center of the tubing measured temperatures at the inlet and near the middle of the upper and lower reactor zones.
  • Comparative Examples C2-C6 were carried out by feeding an aqueous solution of FTHF, ammonia and hydrogen to the above-described liquid overflow, continuous operation apparatus which contained 170.5 g (about 200 mL) of a supported, molybdenum-promoted, nickel catalyst containing approximately 50 weight percent nickel.
  • the total amount of FTHF aqueous solution fed varied from 246 to 288 g.
  • Relative selectivity is the normalization of the 4 major products and disregards 2-(aminomethyl)tetrahydrofuran (tetrahydrofurfurylamine) which forms as a result of 2-formyltetrahydrofuran present in the feed material.
  • These relative selectivities (wt. percentages) and concentrations of Ni and Mo (ppm) are shown in Table II.
  • AMTHF (552 g, 98.3% pure, 5.37 mol) was obtained for an overall yield of 82.5% based upon the amount of FTHF fed to the continuous liquid overflow reactor.
  • material from Examples 6, 7, 9 and 10 were combined and distilled using a 30 plate Oldershaw column to give AMTHF in 89.2% yield with a purity of 98.6%. No solids were observed in either distillation.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Furan Compounds (AREA)

Abstract

L'invention concerne un procédé conçu pour la préparation d'une amine, qui consiste à mettre en contact, dans une zone de réaction, un aldéhyde soluble dans l'eau, de l'ammoniac et de l'hydrogène, en présence d'un catalyseur au ruthénium supporté à une température et une pression élevées. Le procédé, particulièrement utile pour la préparation de 3-(amino-méthyle)tétrahydrofuranne, consiste à mettre en contact une solution aqueuse de 3-formyltétrahydrofuranne avec de l'ammoniac et de l'hydrogène à une température et une pression élevées, en présence d'un catalyseur au ruthénium supporté. On a découvert que l'utilisation dudit catalyseur permettait d'éviter le problème de la lixiviation du catalyseur que l'on rencontre lorsqu'on utilise un catalyseur à base de nickel.

Claims (5)

  1. Procédé pour la préparation d'une amine à partir d'un aldéhyde soluble dans l'eau qui comprend la mise en contact dans une zone de réaction d'un aldéhyde soluble dans l'eau, d'eau, d'ammoniaque et d'hydrogène en présence d'un catalyseur de ruthénium sur support à une température de 60 à 150°C et à une pression totale de 700 à 5 000 kPa, dans lequel le catalyseur de ruthénium sur support comprend de 0,5 à 10 % en poids de ruthénium, rapportés au poids total du catalyseur sur support, et l'amine est le 3-(aminométhyl)tétrahydrofuranne.
  2. Procédé selon la revendication 1, dans lequel la zone de réaction est maintenue à une température de 70 à 120°C et à une pression totale de 1 000 à 3 000 kPa et l'aldéhyde soluble dans l'eau a une solubilité dans l'eau d'au moins 20 g/l.
  3. Procédé selon la revendication 1, dans lequel l'aldéhyde soluble dans l'eau est le 3-formyltétrahydrofuranne et le catalyseur de ruthénium sur support comprend de 5 à 9 % en poids de ruthénium sur un matériau de support de carbone.
  4. Procédé selon la revendication 1, dans lequel la quantité d'eau présente fournit un rapport massique eau:aldéhyde de 0,1:1 à 10:1.
  5. Procédé selon la revendication 4, dans lequel la zone de réaction est maintenue à une température de 70 à 120°C et à une pression totale de 1 000 à 3 000 kPa ; le catalyseur de ruthénium sur support comprend de 5 à 9 % en poids de ruthénium sur un matériau de support de carbone ; et la quantité d'eau présente fournit un rapport massique eau:aldéhyde de 0,2:1 à 2:1.
EP99958664A 1998-10-23 1999-10-22 Preparation d'amines Expired - Lifetime EP1123270B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US178110 1988-05-31
US09/178,110 US5990323A (en) 1998-10-23 1998-10-23 Preparation of amines
PCT/US1999/024776 WO2000024703A1 (fr) 1998-10-23 1999-10-22 Preparation d'amines

Publications (2)

Publication Number Publication Date
EP1123270A1 EP1123270A1 (fr) 2001-08-16
EP1123270B1 true EP1123270B1 (fr) 2003-12-10

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EP99958664A Expired - Lifetime EP1123270B1 (fr) 1998-10-23 1999-10-22 Preparation d'amines

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US (1) US5990323A (fr)
EP (1) EP1123270B1 (fr)
JP (1) JP2002528430A (fr)
DE (1) DE69913556T2 (fr)
WO (1) WO2000024703A1 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100848977B1 (ko) * 2004-06-14 2008-07-30 미쓰이 가가쿠 가부시키가이샤 3－아미노메틸테트라히드로푸란 유도체의 제조방법
KR20080014151A (ko) * 2004-06-14 2008-02-13 미쓰이 가가쿠 가부시키가이샤 3－시아노테트라히드로푸란 유도체의 제조방법
US7700808B2 (en) * 2005-12-26 2010-04-20 Nissan Chemical Industries, Ltd. 1-3-bis(substituted phenyl)-3-hydroxypropan-1-one or 2-propen-1-one compound, and salt thereof
DK2162416T3 (en) * 2007-05-18 2019-02-11 Biofuel Solution I Malmoe Ab GAS PHASE PROCEDURE FOR PREPARING MONOAL ALCOHOL FROM GLYCEROL
US8137527B1 (en) 2008-07-28 2012-03-20 Primafuel, Inc. Carbon dioxide isolation and generation
US20110224470A1 (en) * 2008-11-05 2011-09-15 Biofuel-Solution Ab Process for preparing lower hydrocarbons from glycerol
CN102241652A (zh) * 2011-05-18 2011-11-16 湖南亚帝科技有限公司 结晶紫内酯的制备方法
CN102241649A (zh) * 2011-07-08 2011-11-16 陈飞 3-四氢呋喃甲醇的制备方法
CN109438396B (zh) * 2018-10-31 2020-11-13 山东新和成药业有限公司 一种四氢呋喃-3-甲胺的制备方法
CN110606806B (zh) * 2019-10-04 2022-07-08 重庆工商大学 一种纳米钌催化合成伯胺的方法
CN113717054A (zh) * 2020-05-25 2021-11-30 中国科学院大连化学物理研究所 一种醛还原胺化制备伯胺的方法
CN114621108B (zh) * 2020-12-08 2023-01-13 中国科学院大连化学物理研究所 一种乙醛酸制备甘氨酸的方法
CN116102437A (zh) * 2022-12-23 2023-05-12 南京红宝丽醇胺化学有限公司 一种3-氨基丙醇的制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3843792A1 (de) * 1988-12-24 1990-07-05 Basf Ag Verfahren zur herstellung von 6-aminocapronsaeureestern
DE3843791A1 (de) * 1988-12-24 1990-07-05 Basf Ag Verfahren zur herstellung von caprolactam
ES2077092T3 (es) * 1990-03-30 1995-11-16 Basf Ag Procedimiento para la obtencion de pentano-1,5-diaminas 2,2-disubstituidas.
DE4400591A1 (de) * 1994-01-12 1995-07-13 Basf Ag Verfahren zur Herstellung von Aminoalkoholen
JP3208298B2 (ja) * 1995-10-13 2001-09-10 三井化学株式会社 ３−（テトラヒドロフリル）メチルアミンの製造法

Also Published As

Publication number Publication date
EP1123270A1 (fr) 2001-08-16
JP2002528430A (ja) 2002-09-03
DE69913556D1 (de) 2004-01-22
WO2000024703A1 (fr) 2000-05-04
DE69913556T2 (de) 2004-06-03
US5990323A (en) 1999-11-23

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